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61 Fall 2007

Separable Systems

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QUANTUM IN
1D Systems
ˆ x ˆ=� d p i dx ⎡ ⎤ = i� ˆ, p ˆ⎦ ⎣x

: SEPARABLE SYSTEMS
� � � ˆ = (x ˆ y ˆ z ˆ+jy ˆ+k z ˆ) = i x ˆ r �� ∂ �� ∂ �� ∂ ˆ= p ˆx p ˆy p ˆz = i p +j +k i ∂x i ∂y i ∂y

3D Systems

(

)

⎡ ˆ, p ˆx ⎤ ⎣x ⎦ = i�

⎡y ˆ, p ˆy⎤ = i� ⎣ ⎦

⎡ ˆz ⎤ ˆ, p ⎣z ⎦ = i�

ˆ 2 −� 2 d 2 ˆ= p T = 2m 2m dx 2 ψ (x)
ˆ = O ˆ ψ ( x ) dx ∫ψ ( x ) O
*

ˆ 2 −� 2 ∂ 2 −� 2 ∂ 2 −� 2 ∂ 2 ˆ= p T = + + 2m 2m ∂x 2 2m ∂y2 2m ∂y 2 ψ ( x, y, z )
ˆ = O ˆ ψ ( x, y, z ) dx dy dz ∫ψ ( x, y, z ) O
*

By fiat, operators corresponding to different axes commute with one another.

ˆ ˆ = yx ˆˆ xy

ˆzy ˆ = yp ˆˆz p

ˆz p ˆx = p ˆx p ˆz p

etc.

Further, operators in one variable have no effect on functions of another: ˆ ( y) = f ( y) x ˆ ˆz f ( x) = f ( x) p ˆz ˆx = p ˆ x f * ( z ) etc. xf p f * (z) p The Time Independent Schrödinger Equation becomes:

⎡ �2 ⎛ ∂ 2 ⎤
∂2 ∂2 ⎞ ˆ ˆ ˆ − + + + V x , y , z ( ) ⎢ ⎥ψ ( x, y , z ) = Eψ ( x, y , z )
⎜ 2 2 2 ⎟ 2 m ∂ x ∂ y ∂ z ⎝ ⎠ ⎣ ⎦ ∇ 2 the Laplacian

⎡ �2 2 ⎤ ˆ, y ˆ, z ˆ ) ⎥ψ ( x, y , z ) = Eψ ( x, y , z ) ⎢ − 2m ∇ + V ( x ⎣ ⎦
�2 2 ˆ ˆ, y ˆ, z ˆ ) Hamiltonian operator in 3D ∇ +V ( x H =− 2m

ˆψ ( x, y , z ) = Eψ ( x, y , z ) H
Separation of variables

3D Schrödinger equation (Time Independent)

z )= ψ x (x )ψ y (y )ψ z (z ) (separation of variables) Where we assume that the 1D functions satisfy the appropriate 1D TISE: ˆ ψ ( x) = E ψ ( x) H x x x x ˆ ψ ( y ) = E ψ ( y ) H y y y y ˆ ψ ( z ) = E ψ ( z ) H z z z z First term: ˆ ψ ( x )ψ ( y )ψ ( z ) = ψ ( y )ψ ( z ) H ˆ ψ ( x ) = ψ ( y )ψ ( z ) E ψ ( x ) H x x y z y z x x y z x x = E xψ x ( x )ψ y ( y )ψ z ( z ) Same for ˆ H y and ˆ H z ⇒ ˆ H = E ψ ψ ˆ ˆ ˆ ⎤ ψ ( x )ψ ( y )ψ ( z )⎤ = ( E + E + E ) ⎡ψ ( x )ψ ( y )ψ ( z )⎤ ⎡H y z x y z ⎣ x y z ⎣ x ⎦ ⎦ ⎣ x + H y + Hz ⎦ ⎡ E = Ex + E y + Ez Thus. if the Hamiltonian has this special form. y . the eigenfunctions of the 3D Hamiltonian are just products of the eigenfunctions of the 1D Hamiltonian and the situation is equivalent to doing three separate 1D problems. y ˆ.5. z ˆ ) + Vy ( y ˆ ) + Vz ( z ˆ ) = Vx ( x ˆ) V (x ⎡ �2 ∂ 2 ⎤ ⎡ �2 ∂ 2 ⎤ ⎡ �2 ∂ 2 ⎤ ˆ ˆ ˆ ˆ + + − + + − + H ( x. y. y . ˆ is separable into Conclusion: Wavefunctions multiply and the energies add if H . z ) Then try solution of form ψ (x . y.61 Fall 2007 Separable Systems page 2 IF ˆ. z ) = Eψ ( x. becomes: ˆ ˆ ˆ ⎤ ⎡H ⎣ x + H y + H z ⎦ψ ( x. z ) = ⎢ − V x V y V z ( ) ( ) ( ) x y z ⎥ ⎢ 2m ∂y 2 ⎥ ⎢ 2m ∂z 2 ⎥ 2 then ⎣ 2m ∂x ⎦ ⎣ ⎦ ⎣ ⎦ ˆ ˆ ˆ = H + H + H x y z ⇒ Schrödinger’s Eq.

of H ˆ .mxδ ny . ψ ny . ∫∫∫ψ 111 ( x. z ) dx dy dz ⇒ ∫∫∫ψ 1* ( x )ψ 1* ( y )ψ 1* ( z ) ψ 3 ( x )ψ 1 ( y )ψ 1 ( z ) dx dy dz ⇒ ∫ψ 1* ( x )ψ 3 ( x ) dx ∫ψ 1* ( y )ψ 1 ( y ) dy ∫ψ 1* ( z )ψ 1 ( z ) dz = 0 * x y z x y z x x y y z z 0 x 1 x 1 Because the product states are orthogonal and normalized.mz ∫∫∫ ( ) ( ) Example 1:3­D Harmonic Oscillator Let’s consider a particle in 3D subject to a Harmonic potential in x. of H x ˆ and any eigenfunction. z ) = ψ x 3 ( x )ψ y1 ( y )ψ z1 ( z ) . Multidimensional . Further. z )ψ 311 ( x. y. y. consider the two wavefunctions ψ 111 ( x. ψ n . z ψ mxmymz x. For example. ψ nx . z dx dy dz = δ nx . for a particle trapped inside a protein: the resorting force for moving it in the x direction will be different from y or z because the protein has a different shape along x than y or z (see below right). we do not have to have all three 1D functions be different. y. for two product states to be orthogonal. while in 1D we usually had one quantum number. This might be true. y.y or z) is orthogonal to its counterpart. together with any eigenfunction. H x y z The 3D product states are naturally normalized if the 1D wavefunctions are normalized: ∫∫∫ψ ( x )ψ ( y )ψ ( z )ψ ( x )ψ ( y )ψ ( z ) dx dy dz = * * * x y z x y z ∫ψ ( x )ψ ( x ) dx ∫ψ ( y )ψ ( y ) dy ∫ψ ( z )ψ ( z ) dz = 1 * * * x x y y z z 1 x 1 x 1 ˆ Notice that for ψ we are free to choose any eigenfunction. y. then the two 3D wavefunctions are also orthogonal.nz).myδ nz .61 Fall 2007 Separable Systems page 3 ˆ =H ˆ +H ˆ +H ˆ . If any one of the three 1D wavefunctions (x. they’re orthonormal and we summarize this by writing: ψ nxnynz * x. in 3D we will have three (nx. for example.of H y z z Thus. Further.ny. z ) = ψ x1 ( x )ψ y1 ( y )ψ z1 ( z ) and ψ 311 ( x. assume the force constants in each direction are different.5.y and z. y.

we can immediately write down all the eigenfunctions and eigenvalues: ψ n n n ( x . there are a number of interesting things that can happen that we didn’t see in 1D. we can easily write the Hamiltonian down as a sum: ˆ =H ˆ +H ˆ +H ˆ H x y z ˆ x2 1 p ˆ ˆ2 + kx x Hx = 2m 2 ˆ y2 1 p ˆ ˆ 2 + ky y Hy = 2m 2 ˆ z2 1 2 ˆ = p ˆ + kz z H z 2m 2 where each 1D Hamiltonian describes a particle subject to a Harmonic potential with the appropriate spring constant (kx. Degeneracies In 3D. a y potential and a z potential.5. Based on the discussion above. because the potential is a sum of an x potential. y . and the energy and wavefunction depend on all three simultaneously. in HCO x might correspond to the CH stretch. One example of this is that. ky or kz).61 Fall 2007 Separable Systems page 4 Harmonic potentials are also important for describing the vibrations of polyatomic molecules. In either case. m Notice again that for the 3D problem we have 3 quantum numbers. in 3D it is possible for two different . the general potential is given by V ( x. For example. z ) = 1 1 1 k x x 2 + k y y 2 + k z z 2 = V x ( x ) + V y ( y ) + Vz ( z ) 2 2 2 Now. y to the C­O stretch and z to the H­C­O bend. z ) = N x H n (α x x ) e 1/2 x y z x − α x x2 2 N y H n y (α y y ) e 1/2 − α y y2 2 − ⎛ αz ⎞ 1/2 N H z e α ( ) z nz z ⎜ ⎟ ⎝π ⎠ 1 4 α z z2 2 1⎞ 1⎞ 1⎞ ⎡⎛ ⎤ ⎡⎛ ⎤ ⎡⎛ ⎤ Enxn y nz = ⎢⎜ n x + ⎟ �ωx ⎥ + ⎢⎜ n y + ⎟ �ω y ⎥ + ⎢⎜ n x + ⎟ �ωz ⎥ 2⎠ 2⎠ 2⎠ ⎣⎝ ⎦ ⎣⎝ ⎦ ⎣⎝ ⎦ ( mk x ) αx = � 12 ωx = kx etc. y .

This never happened for the Particle in a Box or the Harmonic Oscillator. say ψ ( x.61 Fall 2007 Separable Systems page 5 eigenfunctions of the Hamiltonian to have the same energy. z ) . these two states are called degenerate. z ) = a ψ 010 ( x. four… states with the same energy. one can show that for bound states in 1D. so it is not degenerate. y . y . However. If there are three. However. n x = 0. in 3D we can find degeneracy very easily. z ) ≠ ψ 001 ( x. z ) ≠ ψ 010 ( x. In fact. ny = 0. When this happens. y .5. every state has its own energy. nz = 0 ). they are said to be threefold. We will typically draw this with a picture like: E E110 E011 E100 E101 … E200 E020 E002 6­fold degenerate E010 E000 E001 3­fold degenerate Non­degenerate Note the wavefunctions are distinct: ψ 100 ( x. So we find that if we choose all the E000 = 3�ω 2 5�ω 2 nondegenerate level 3-fold degenerate level E100 = E010 = E001 = etc. there are three ways I can get the first excited state energy spring constants to be equal. ny = 1. n y = 0. There is only one way I can get this energy ( n x = 0. For example. z ) This leads to an interesting effect. y. z ) + b ψ 001 ( x. ny = 0. if our spring constants are all the same: kx = k y = kz ≡ k ⇒ ωx = ω y = ωz ≡ ω 3⎞ ⎛ ⇒ Enxn y nz = �ω ⎜ n x + n y + n z + ⎟ 2⎠ ⎝ 3 The ground state has an energy E000 = 2 �ω . nz = 0 or n x = 0. nz = 0 . nz = 1 . 5 2 �ω : n x = 1. Suppose we make up a wavefunction that is a sum of two degenerate states. fourfold … degenerate. y. y . one never has degeneracy.

because the force constants are slightly different. Then it turns out that ψ is also an eigenstate of the Hamiltonian! To see this.5. but not quite. Setting the spring constants equal amounts to assuming the well is symmetric with respect to x. y and z.e. we will usually say that the degeneracy has been “lifted” or that the degenerate states have been split. Notice that it is possible to break some degeneracies but keep others. i. if we choose: kx = k y ≡ k ≠ kz Then the energies become: ⇒ ωx = ω y ≡ ω ≠ ωz 1⎞ ⎛ Enxn y nz = �ω ( n x + n y + 1) + �ωz ⎜ nz + ⎟ 2⎠ ⎝ and we find . then the energy levels might look like: E E110 E011 E100 E101 E200 E020 E002 E010 E000 E001 Here. ˆψ = H ˆ (a ψ + b ψ ) = a H ˆψ + b H ˆψ H 010 001 010 001 =a 5 �ω 2 ψ 010 + b 5 �ω 2 ω ψ 001 = 5� 2 ( a ψ 010 + b ψ 001 ) ω = 5� 2 ψ This illustrates the important point that any sum of degenerate eigenstates is also an eigenstate of the Hamiltonian with the same eigenvalue. If the symmetry is “broken”. k x ≠ k y ≠ k z then the 100.61 Fall 2007 Separable Systems page 6 where a and b are constants. In this case. 010 and 001 states will become non­degenerate. you can see that the n=1 levels are almost degenerate (they’ve been “split”) and the n=2 levels are almost degenerate. For example . The latter language comes from the pictorial view. if the spring constants are only slightly different.

61 Fall 2007 Separable Systems page 7 1 E000 = �ω + �ωz 2 1 E100 = E010 = 2�ω + �ωz 2 3 E001 = �ω + �ωz 2 nondegenerate level 2-fold degenerate level nondegenerate level .5.

z )= 0 ˆ =H ˆ +H ˆ +H ˆ where We can again apply separation of variables since H x y z ˆ . z ) = ψ n ( x )ψ n x y ( y )ψ n ( z ) z where from the 1D problem we have the solutions ⎛n πx⎞ ⎛2⎞ ψ nx ( x ) = ⎜ ⎟ sin ⎜ x ⎟ ⎝a⎠ ⎝ a ⎠ ⎛n πy⎞ ⎛ 2 ⎞2 ψ n y ( y ) = ⎜ ⎟ sin ⎜ y ⎟ ⎝b⎠ ⎝ b ⎠ ⎛2⎞ ⎛n πz⎞ ψ nz ( z ) = ⎜ ⎟ sin ⎜ z ⎟ ⎝c⎠ ⎝ c ⎠ 1 2 1 1 2 n x = 1. 2 �2 nx En x = 8m a 2 �2 n y En y = 8m b2 � 2 nz2 En z = 8m c 2 2 nz = 1. y . Where the energy is now a function of all three Quantum numbers: . 2. 2. y ...Vz ( z ) = ∞ Outside the box: − �2 ⎛ ∂ 2 ∂2 ∂2 ⎞ + + ψ ( x. So the solutions to the H x y z 3D equation are products of the 1D solutions ⇒ ψ ( x .61 Fall 2007 Separable Systems page 8 Example 2: Particle in 3­D box z c V ( x... z ) = Eψ ( x. 2.3. z ) = Vx ( x ) + V y ( y ) + Vz ( z ) Vx ( x ) = 0 Vy ( y ) = 0 Vz ( z ) = 0 a x Inside the box: 0≤ x≤a 0≤ y≤b 0≤ z≤c otherwise b y Vx ( x ) . y .3. z ) 2 2 2 ⎟ 2m ⎜ ∂ x ∂ y ∂ z ⎝ ⎠ ψ (x .3.H ˆ are each 1D particle in a box Hamiltonians.5... n y = 1..H ˆ .V y ( y ) .. y . y..

g.61 Fall 2007 Separable Systems page 9 En x n y n z Degeneracies 2 n2 �2 ⎛ nx nz2 ⎞ y = E n x + E n y + E nz = ⎜ 2+ 2+ 2⎟ 8m ⎜ b c ⎟ ⎝a ⎠ Degeneracies occur in a similar fashion for the PiB. e. z ) = ψ 1 ( x )ψ 1 ( y )ψ 1 ( z ) = ⎜ 3 ⎟ sin ⎜ ⎟ sin ⎜ ⎟ sin ⎜ ⎟ ⎝a ⎠ ⎝ a ⎠ ⎝ a ⎠ ⎝ a ⎠ But… E211 = E121 = E112 h2 = 22 + 12 + 12 ) 2 ( 8ma 3­fold degeneracy Note the wavefunctions are again distinct: ψ 211 (x.5. z ) E E222 E221 E211 E212 E121 E111 E122 E112 Non­degenerate Non­degenerate 3­fold degenerate . y . z )≠ ψ 121 (x . y . if a = b = c in our 3­D box: ⇒ En x n y n z = h2 2 n2 + n2 y + nz ) 2 ( x 8ma 3h 2 E111 = 8ma 2 is nondegenerate 1 ⎛ 8 ⎞2 ⎛π x ⎞ ⎛π y ⎞ ⎛π z ⎞ ψ 111 ( x. y . z )≠ ψ 112 (x . y .

5. 2. a≠ b≠c then the degeneracy is lifted. n y = 1. . i..3. E112 h2 ⎛ 1 1 4 ⎞ h2 ⎛ 1 4 1⎞ = ⎜ 2 + 2 + 2 ⎟ ≠ E121 = ⎜ 2+ 2+ 2⎟ 8m ⎝ a 8m ⎝ a b c ⎠ b c ⎠ Summary 3­D box ⎛ 8 ⎞2 ⎛ n xπ x ⎞ ⎛ n yπ y ⎞ ⎛ n zπ z ⎞ ψ nx n y nz ( x .3.. nz = 1.... z ) = ⎜ ⎟ sin ⎜ ⎟ sin ⎜ ⎟ ⎟ sin ⎜ ⎝ abc ⎠ ⎝ a ⎠ ⎝ b ⎠ ⎝ c ⎠ En x n y n z 2 n2 h 2 ⎛ nx nz2 ⎞ y = ⎜ 2+ 2+ 2⎟ 8m ⎜ b c ⎟ ⎝a ⎠ 1 n x = 1. y . 2.61 Fall 2007 Separable Systems page 10 If the symmetry is “broken”.....e. 2.3.